SPECTROSCOPIC AND THERMOCHEMICAL PROPERTIES OF ACTINIDE-CONTAINING SPECIES FROM FIRST PRINCIPLES: THORIUM AND AMERICIUM MONOXIDE MOLECULES

Abstract

A relativistic version of a composite ab initio treatment of molecular spectroscopy and thermochemistry is developed, focusing on high-accuracy description of the properties of actinide (An) containing species. It is based on combining the calculation results at levels of theory with sufficiently full account of electron correlation, e.g., at the CCSDT(Q) level, but tackling only scalar relativity, with those obtained from more rigorous four-component relativistic calculations with the Dirac–Coulomb Hamiltonian. High accuracy achievable via this approach is revealed taking the examples of thorium and americium monoxide molecules. The errors in ab initio values for the bond length re, vibrational frequency ωe, and atomization energy D0 of the ThO molecule did not exceed 0.001 Å, 2.5 cm–1, and 0.5 kcal/mol, respectively. The composite numerical values for the first ionization potentials of the AmO molecule and the Am atom deviate from the experimental data just by 0.03 eV and 1 cm–1, respectively. For the first time, the proposed approach enabled high-accuracy evaluation of the molecular constants re, ωe and D0 for AmO and AmO+, as well as the second and third ionization potentials of the Am atom. The calculation results are indicative of a minor actinide contraction of the An–O bonds on going through the molecular series ThO → UO → AmO: the bond length in AmO is by 0.0073 Å shorter than that in ThO. The re(An–O) value is shown to be linearly dependent on the actinide atomic number in the periodic table. The results obtained may be used as benchmarks for parametrizing and calibrating the DFT functionals designed for treating An-containing molecules.